Swelling Poly (Ionic Liquid)s: Heterogeneous Catalysts That are Superior than Homogeneous Catalyst for Ethylene Carbonate Transformation

Abstract

Heterogeneous catalysts usually show much lower catalytic activities than homogeneous catalysts due to insufficient dispersion and contact of catalytically active sites to reactants. Efforts have been made to solve this problem during past decades. Herein, we have synthesized a series of poly (ionic liquid)s (PILs), which are well swelled in ethylene carbonate (EC), by polymerization of N‐vinylimidazolium ionic liquid monomers with divinylbenzene (DVB). The structure, morphology and swelling property of the PILs were charicreized by 13C MAS NMR, FT‐IR and SEM. Cyro‐SEM showed that the PILs demonstrate a 3D network structure in swelling state which might promote mass transfer and dispersion of active sites. The PILs were utilized in the reaction of 2‐(phenylamino) ethanol (2‐PAE) and EC and exhibited even better catalytic performance than homogeneous catalyst 1‐butyl‐3‐methyl‐imidazolium acetate (BmimOAc). This superior catalytic activity is strongly related to the swelling property and selective absorption behavior of PILs. The absorption behavior was investigated by 1H NMR analysis of mole ratio of reactants to product inside and outside of PILs in the reaction mixture. It was found that the PILs could enrich reactants and eject products which could accelerate the reaction.

Honeycomb-structured solid acid catalysts fabricated via the swelling-induced self-assembly of acidic poly(ionic liquid)s for highly efficient hydrolysis reactions

“…Recently, we developed a series of carboxylate-based poly(ionic liquid)s (PILs) with high swelling abilities in ethylene carbonate [26][27][28]. These PILs were used as efficient catalysts for the transformation of ethylene carbonate, and their activity was comparable with that of the corresponding homogeneous ILs.…”

Cooperative Catalysis of Ru(III)‐Porphyrin in CO2‐Involved Synthesis of Oxazolidinones

“…It has been well known that the reactions of CO 2 with different amino compounds can produce various organic chemicals, such as urea, [13,14] bis‐substituted urea, [15] carbamates [16–18] (Scheme 1, Eq. 1–3) and oxazolidinones (i. e., cyclic urethanes), [19–25] revealing that the activation of CO 2 by alkaline amino‐compounds in cooperative combination of a suitable catalyst is of fundamental importance in CO 2 ‐involed synthesis protocols. As for the synthesis of oxazolidinones via CO 2 ‐fixation using high‐energy N‐containing compounds (such as ethanolamines, aziridines or ethylene epoxide) featured with strict structural limitation (Scheme 1, Eq.…”

“…As for the synthesis of oxazolidinones via CO 2 ‐fixation using high‐energy N‐containing compounds (such as ethanolamines, aziridines or ethylene epoxide) featured with strict structural limitation (Scheme 1, Eq. 4,5), [19–21] the application of simple amines was advantageous with structural variety, low‐cost, and facile manipulation (Scheme 1). Encouragingly, the three‐component reaction of CO 2 , aromatic amines and 1,2‐dihaloethane have been reported with the presence of carefully selected organocatalyst, [22,23] wherein the nucleophilic substitution of the involved aromatic amines with haloalkanes was the rate‐determining step (Scheme 1, Eq.…”

Functional mesoporous poly (ionic liquid) derived from P123: From synthesis to catalysis and alkylation of styrene and o‐xylene

“…Recently, a series of PIL materials have been synthesized by introducing functional cationic and anionic IL groups into dynamic macromolecular polymeric architectures which have broadened PIL properties, structures, functionalities and applications . PILs have been widely used in catalysis due to the function‐designability and eco‐friendly quality . For example, Ali Pourjavadi and cooperators synthesized a dual acidic heterogeneous organocatalyst by copolymerization of acidic ionic liquid monomer ([VSim][HSO 4 ]) and liquid crosslinker (1,4‐butanediyl‐3,3‐bis‐l‐vinyl imidazolium dihydrogen sulfate) .…”